Process of making a water dispersible coating vehicle



Patented July 1, 1947 PROCESS OF MAKING A WATER DIS- PERSIBLE COATING VEHICLE George E. Eilerman, Milwaukee, Wis., assignor to Pittsburgh Plate Glass Company, Allegheny County, Pa., a corporation of Pennsylvania No Drawing. Application December 10, 1943, Serial No. 513,727

2 Claims.

The present invention relates to the prepara- I tion of paint vehicles which are emulsifiable in water, and it has particular relation to the preparation of such vehicles from linseed oil or other drying oil.

The objects of the invention comprise the provision of a water en ulsiiiablgpaint yehicle which forms relatively h ard, water resistant and durable films; which easily forms water emulsions stable and durable over long periods of time; which forms pastes having good wetting qualities; and which is relatively inexpensive to prepare.

These and other objects will be apparent from consideration of the following specification and claims.

It has heretofore been proposed to prepare paints embodying a suitable vehicle emulsified in water. When these paints were spread as films, the water quickly evaporated leaving the vehicle in place and in comparatively hard state. Emulsion paints possessed many virtues. They were inexpensive, set very quickly and were free of objectionable odors. However, the films were not usually so hard as might be desired. Their water resistance, especially in washing was low and in many instances pastes and emulsions were not stable upon standing.

The use of resin emulsion vehicles in present paint manufacturing facilities demands certain properties of the resin emulsion. Such vehicle must withstand any of the heating operations involved in mixing or grinding or paste paints without sacrificing any of their properties of workability. It is important that such vehicles wet" the surfaces of grinding equipment to insure proper incorporation of pigments and inerts.

A satisfactory esinemulsionvehicle must not undergo any markedchangs or inversion of phase on dilution. The wetting properties of a resin emulsion vehicle that may be desirable as a water in oil emulsion must not change on inverting the emulsion to an oil in water type on dilution. Any change in the wetting of the resin emulsion vehicle will prevent the even distribution of the resin and form a discontinuous film on application.

A satisfactory resin emulsion should have stability. An unstable emulsion vehicle will separate on standing into phases, one of which will cake and be difficult to redistribute. This instability is more marked on formulated paste paints.

It must dry well on application but still show no signs of skinning as an emulsion.

It must not show excessive foaming on dilution.

It must have a viscosity high enough to allow for a desirable pigment to binder ratio and still permit easy brushing.

It must dilute with water easily and must be easily removed from a paint brush.

It must dry to a water-insoluble film with a certain degree of sm'face hardness.

A satisfactory resin emulsion vehicle can now be prepared from hydrolyzed maleinized linseed oil, hydrolyzed malei ze a resins, or n general from hydrolyzed maleim'zed natural or synthetic dryin 01 s, W1 "and ammonium h organic amine. "Maleinized ol l is e ned as en um pro uc of malec anhydride and any oil d in natural or s thetic. Hydrolysis of the maleinized oil is the chemical reaction of opening the anhydride linkage of the maleic anhydride residue with the elements of water.

Preparation of water emulsion vehicle A mixture of 2195 parts of linseed oil and about 8 to e. g., 245 parts of maleic anh dride was heated to 250 C. and held at this temperature for five hours. This maleinized oil was then cooled to 130 C. and 45 parts of water was added. Heating at this temperature was continued for one hour to insure complete hydrolysis of the anhydride addition product. At C. this vehicle will have a viscosity of 2-1 (Gardner) and an acid number of 89.2.

300 parts of the above maleinized oil and 9.4 parts of drier solution were intimately mixed. A mixture of par s of water and parts of a water-sglublesilicate (e. g. sodium or potassium),

or e a e, so ium silicate solution Z3! Baum and 8.9% Na 2 was epare an added 0 e oil-drier solution. This entire mass was stirred for about 30 minutes during which time the mixture became thick and appeared grainy. If the stirring is rapid and the time lengthened, this material will become more homogeneous and the precipitate will be more finely divided. This mixture was still acid to litmus and a water-soluble basic nitrogen compound, e. g. 27 parts of ammonium hydroxide (28% NH: sp. gr. 0.9) was added to neutralize the mass completely.

Alcoholysis products of maleinized oil and a1- cohols may also be used with sodium silicate soTiT- tion to prepare satisfactory resin emulsion vehicles. Alcohols that may be used for such products include the monohydric alcohols, methyl, ethyl, propyl, etc.; the dihydric lcohoE, ethylen'il'ycmthylene 1 col, triethylene lycol, tetraetfiylene gl col etc.; the 'polyhydric alco ols, ero, pentaerythritol, mannitol, etc. In prepamse products Hie alcohol is used to rupture the anhydride linkage of the maleinized oil.

A satisfactory paste paint can be prepared from the above vehicle. The principal characteristic about the above vehicle is the property of wetting. A dilution of two parts of water to one of so ium siica 9 so ution e or any water soluble the above vehicle can still be painted on sealed surfaces an e film deposited on the surface will be continuous before and after dry g. Such a film will dry and no longer be soluble in water. If the odor of ammonia is objectionable in the above formulation, small amounts of acids such as oleic, stearic, linseed oil acids, rosin, acidic gums, etcf'n ia'i be added to neutraillie'in'yl'i'ee present. Furthermore, since it is desirable to have a certain brushing viscosity on dilution of any finished paste paint, the viscosity of the original vehicle is reinforced with small amounts of alginates, gums, milk casein, or soy protein.

Preparation of paste A typical paste was prepared from this vehicle substantially as follows:

666 parts of the above vehicle of 48% total solids was mixed with 11 g. e acid, 150 parts of 1% ammonium alginate solution and 123 parts of wa r give an emu sion vehicle of 35% total solids.

1.3 lb. of the above vehicle (35% total solids),

50.5 lb. titanium dioxide, and 0.8 lb. talc was compounded on a three-roll mill. The res flung paste on dilution of two parts of paste to one of water gave a paint, the viscosity of which was between and 30 seconds from a full Ford cup.

In the preparation of the emulsion vehicle, the amounts of sodium silicate solution and concentrated ammonium hydroxide may be used in different proportions to accomplish the same result; that is, emulsions have been prepared in which the acidity of the hydrolyzed maleinized oil has been neutralized by such combinations: 15% sodium silicate solution, 85% concentrated ammonium hydroxide; sodium silicate solution, 5% concentrated ammonium hydroxide; 50% sodium silicate solution, 50% concentrated ammonium hydroxide; 75% sodium silicate solution, 25% concentrated ammonium hydroxide. The larger the amount of sodium silicate solution, the less the gloss of the dried film. This elimination of gloss in the vehicle is of particular advantage in the preparation of flat wall paints.

Many water-soluble amines can be substituted for the concentrated ammonium hydroxide. The following vehicles are illustrative:

Grams Hydrolyzed maleinized linseed oil (described above) 100 Drier solu 3.1 Water containing 6.8 g. sodium silicate solution Water containing 6.5 g. morpholine 50 Grams Hydrolyzed maleinized linseed oil 100 .Drier solu n 3.1 .Water containing 6.8 g. sodium silicate solution 200 Water containing 6.7 g. 2-methyl-2-amino- 1 propanol 50' Grams Hydrolyzed maleinized linseed oil 100 Drier solu 3.1 Water containing 6.8 g. sodium silicate solution 200 Water containing 4.6 g. monoethanolamine 50 Grams ydrolyzed maleinized linseed oil 100 ier sol 3.1

5 Water containing 6.8 g. sodium silicate solution 200 Water containing 7.6 g. diethanolamine 50 m Grams Hydrolyzed maleinized linseed oil 100 Drier sol 3.1 Water containing 6.8 g. sodium silicate solution 200 15 Water containing 11.2 g. triethanolamine 50 Grams Hydrolyzed maleinized linseed oil 100 20 Drier soluti 3.1

Water with 6.8 g. sodium silicate solution 200 Water with 7.9 g, 2-amino-2-methyl-1.3-

Water with 6.8 g. sodium silicate solution 200 Water with 9.1 g. tris (hydroxymethyD- amino-methane 50 All of these vehicles have the desirable properties described above and can be used to prepare a paste paint that can be diluted with water.

The above observations are not limited to the use of maleinized linseed oil. Any wilength alk d resin may be used in place of the linseed oil. The following are examples:

1756 parts of lins i1 and 92 parts of g l y c erine were heated t6'200" C. and 2 g. Of itharge was added. This mixture was held at t is temperature for three hours. 1200 parts of rosin was added and the mixture was heated at 230 C. until the acid number reached 50-55. 300 parts of maleic anh dride was added and the resulting mixture was heated at 200 C. for one hour. The resin mixture was then cooled to 100-130 C. and 60 parts of water added. Heating was continued at this temperature for an additional hour. This vehicle may be used in any of the above formulations for the preparation of paste paints that will dilute with water.

100 parts of this composition can be substituted for maleinized linseed oil in any of Examples A to G inclusive.

Phthalic acid, maleic acid, fumaric acid, tetrahydropfithalic acid. succinic acid, etc., can be su 1 u e proper molecular ratio for rosin in the foregoing example or analogous formulations of long oil length alkyds to provide addendum products with maleic anhydride. which can be hydrolyzed and reacted with sodium silicate. Other alcohols such as glycol, pentaerythrit0l, ethylene glycol, etc., cmomd for W alkyd resins.

Example was added and the reaction was continued at this temperature for one hour. This reaction mixture was then cooled to 100-120 C. and 37 parts of water was added. Heating was continued for one hour. This vehicle may be used in any of the above formulations in place of maleinized linseed oil for the preparation of paste paints that will dilute with water.

China-wood oil, extracted linseed oil, hi h iou'in'soya Bean oil, or any of the s ntHetic dryg o may maleinized, hydrolyzed, and us a e above formulations to prepare resin-emulsion paints. Oils, such as linseed or soya bean, concentrated by the process disclosed in FTeeman Patent 2,200,391 can also be employed.

In the films obtained by use of the vehicles herein disclosed it would appear that at least some of the unsaturated bonds of the maleic anhydride-drying oil reaction product possess 9. capacity for air drying and the films thus set up comparatively hard. They, also, become sufficiently water-resistant to admit of washing.

The embodiments of the invention herein disclosed are to be considered merely as being representative or typical. It will be apparent to those skilled in the art that numerous modifications may be made therein without departure from the spirit of the invention or the scope of the appended claims.

I claim:

1. A process of preparing a resin composition capable of forming a non-skinning emulsion in water, which process comprises neutralizing with sodium silicate and ammonia the adduct of maleic anhydride and a glyceride drying oil, the anhydride rings of said adduct being opened before neutralization.

2. A process as defined in claim 1 in which the opening of the anhydride rings is performed by heating the adduct to a temperature of about C. in the presence of water for approximately one hour.

GEORGE E. EILERMAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,285,646 Clocker June 9, 1942 2,133,759 Vail Oct. 18, 1938 2,051,409 Kenney Aug. 18, 1936 1,998,845 Sardinha Aug. 23, 1935 Examiner 

